Water → Dimethyl 7-chloroquinoline-2,3-dicarboxylate

HRID 1449564

反応式

HRID 1449564 の反応式
Cl[C:2]1[C:11]2[C:6](=[CH:7][C:8]([Cl:12])=[CH:9][CH:10]=2)[N:5]=[C:4]([C:13]([O:15][CH3:16])=[O:14])[C:3]=1[C:17]([O:19][CH3:20])=[O:18].C([O-])=O.[Na+].O>CN(C)C=O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[Cl:12][C:8]1[CH:7]=[C:6]2[C:11]([CH:2]=[C:3]([C:17]([O:19][CH3:20])=[O:18])[C:4]([C:13]([O:15][CH3:16])=[O:14])=[N:5]2)=[CH:10][CH:9]=1

参加物

6

反応物 3

HCID 962WaterHCID 2723810Sodium FormateHCID 18929951Dimethyl 4,7-dichloroquinoline-2,3-dicarboxylate

生成物 1

HCID 18929843Dimethyl 7-chloroquinoline-2,3-dicarboxylate収率 134.8%

試薬・触媒・溶媒 2

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 6228Dimethylformamide溶媒

実験手順

A stirred mixture of dimethyl 4,7-dichloroquinoline-2,3-dicarboxylate (5.00 g, 15.9 mM), sodium formate (1.63 g, 23.9 mM) and tetrakis(triphenylphosphine)palladium(O) (0.92 g, 0.80 mM) in anhydrous dimethylformamide (75 mL) under a nitrogen atmosphere was heated at 90°-95° C. for 7 hr. No reaction occurred so the reaction mixture was degassed and an additional quantity of tetrakis(triphenylphosphine)palladium(O) (0.92 g, 0.80 mM) was added and the reaction mixture again heated at 90°-95° C. for 6 hr. The cooled reaction mixture was poured into water and the resulting mixture extracted with ethyl acetate. The combined extracts were dried (MgSO4), filtered and concentrated to leave an gummy solid (6.0 g). Trituration of this residue with ethyl acetate and subsequent filtration separated a crystalline solid which was shown to be dimethyl 7-chloro-4-hydroxyquinoline-2,3-dicarboxylate. The filtrate was concentrated and the residue was flash chromatographed over silica gel (eluant: hexane/ethyl acetate, 3/2) to provide the title diester (1.13 g, 25.4%) as a light yellow crystalline solid; MS(CI): 280 (M+H). 300-MHz 1H NMR (DMSO d6), 9.15 (s, 1H), 8.33 (d, 1H, J=9 Hz), 8.25 (d, 1H, J=2 Hz), 7.86 (dd, 1H, J=9 Hz, 2 Hz), 3.93 (s, 3H), 3.92 (s, 3H).

後処理

  1. temperaturewas heated at 90°-95° C. for 7 hr
  2. customwas degassed
  3. additionan additional quantity of tetrakis(triphenylphosphine)palladium(O) (0.92 g, 0.80 mM) was added
  4. temperaturethe reaction mixture again heated at 90°-95° C. for 6 hr
  5. customThe cooled reaction mixture
  6. extractionthe resulting mixture extracted with ethyl acetate
  7. dry with materialThe combined extracts were dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated

出典と根拠

ORDレコード
ord-f6907b34b0c342fcb7ba55f380ddb031
出典データセット
uspto-grants-1997_02
特許番号
US05599814

関連ノート

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